IL302430A - Method for stabilizing an organic material using a stabilizer mixture - Google Patents

Method for stabilizing an organic material using a stabilizer mixture

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Publication number
IL302430A
IL302430A IL302430A IL30243023A IL302430A IL 302430 A IL302430 A IL 302430A IL 302430 A IL302430 A IL 302430A IL 30243023 A IL30243023 A IL 30243023A IL 302430 A IL302430 A IL 302430A
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substituted
unsubstituted
linear
branched
compound
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IL302430A
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Basf Se
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Description

WO 2022/096356 PCT/EP2021/079940 1 Method for stabilizing an organic material using a stabilizer mixture Field of the Invention The presently claimed invention relates to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound. The presently claimed invention further relates to a stabilizer mixture comprising at least one compound (A), at least one UV absorber, and at east one metal hydroxide. The presently claimed invention also relates to a composition comprising an organic material, and the stabilizer mixture. Further, the presently claimed invention relates to an article prepared from the said composition. StilI further, the presently claimed invention relates to a use of the stabilizer mixture for stabilizing an organic material by reducing degradation induced by a chlorine containing compound.
Background of the Invention Organic materials namely synthetic polymers such as polyolefins, polyethylenes, and the like are used in wide variety of applications due to their ease of use in the manufacturing of a variety of extruded and moulded articles. Exemplary articles such as greenhouse, mulch film or tapes are prepared using the organic material. However, these articles frequently suffer from general stability due to repeated exposure to the UV light. Sterically hindered amines are known in the art to be efficient stabilizers, preventing the ill effects of UV light on the articles prepared from the organic material. However, these articles when exposed to high level of chlorine containing agrochemicals or bleaching agents are subjected to enhanced degradation which subsequently leads to loss of tensile strength. The major cost factor of greenhouses or artificial turf is the installation. The loss of tensile strength leads to premature damage of greenhouses or artificial turf, causing a lot of effort as well as cost for the replacement.
Thus, it is an object of the present invention to provide a multilayer film with a high stability by reducing the degradation induced by a high level of chlorine containing compounds.
Summary of the Invention Surprisingly, it has been found that the multilayer film prepared in accordance with a method of the presently claimed invention using a certain stabilizer mixtures exhibits a substantia improvement of the elongation at break property and therefore stabilizes the multilayer film by reducing degradation induced by the high level of chlorine containing compounds.
Thus, in one aspect, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having WO 2022/096356 PCT/EP2021/079940 2 a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from genera formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) a wherein A! is selected from linear or branched, substituted or unsubstituted C2-C18 alkylene, substituted or unsubstituted C5-C7 cycloalkylene and C1-C4alkylenedi(C 5-C7cyclo alkylene), a2 is independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12 cycloalkyloxy, A3and A4 are independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c ch3 ch3z c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, compound (A) of general formula (II) WO 2022/096356 PCT/EP2021/079940 (II) wherein x!and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, - compound (A) of general formula (III) (III) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl; and - compound (A) of general formula (IV) (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, WO 2022/096356 PCT/EP2021/079940 4 Y3 is selected from linear or branched, substituted or unsubstituted C3 to C20 alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber; and (iii) at least one metal hydroxide.
In another aspect, the presently claimed invention is directed to a stabilizer mixture comprising: (i) at least one compound (A) selected from the general formula (A-l), generaformula (A-2), genera formula (A-4), general formula (A-5), general formula (A-6),general formula (A-7), and general formula (A-8) (A-4), N H9C4—N------------------"S---------------- N--------- (CH2)6 N N^,N .1 .1 h3cZ Tch= H,CA_Nh3c>C D (A-l), ' -- (A-2), yr x> H-----0 ' N —-------------- N—C4Hg N^,N .CH3 T H3C r 'LCH3 ch3 n-c4h9 H3CXN/^CH3 H3C>L /^CH3 C2H7 H3C CH3 O 63h7 0---------C11H23 0 V-------- c17h35-0 WO 2022/096356 PCT/EP2021/079940 (A-5); (A-6) WO 2022/096356 PCT/EP2021/079940 (A-7), and (A-8) wherein n is 2, (ii) at least one UV absorber; and (iii) at least one metal hydroxide.
In another aspect, the presently claimed invention is directed to a composition comprising: I. an organic material, and II. a stabilizer mixture, wherein the stabilizer mixture comprises at least onecompound (A) is selected from the general formula (A-l), general formula (A- 2), general formula (A-4), general formula (A-5), general formula (A-6), genera formula (A-7), and general formula (A-8), at least one UV absorber, and at least one metal hydroxide.
In another aspect, the presently claimed invention is directed to an article comprising the composition as defined above.
WO 2022/096356 PCT/EP2021/079940 7 In still another aspect, the presently claimed invention is directed to the use of the stabilizer mixture, as defined above, for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having the chlorine content in the range of 100 to 6ppm.
Detailed Description of the Invention Before the present compositions and formulations of the invention are described, it is to be under-stood that this invention is not limited to particular compositions and formulations described, since such compositions and formulation may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the presently claimed invention will be limited only by the appended claims.
If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Further-more, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention de-scribed herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "(A)", "(B)" and "(C)" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless other-wise indicated in the application as set forth herein above or below.
In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Reference throughout this specification to "one embodiment" or "a preferred embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at east one embodiment of the presently claimed invention. Thus, appearances of the phrases "in one embodiment" or "in a preferred embodiment" or "in another embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some, but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the WO 2022/096356 PCT/EP2021/079940 8 scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.
Furthermore, the ranges defined throughout the specification include the end values as well i.e. a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant shall be entitled to any equivalents according to the applicable law.
Certain terms are first defined so that this disclosure can be more readily understood. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention pertain.
In an aspect, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18alkylene, substituted or unsubstituted C5-C7 cycloalkylene and C1-C4alkylenedi(C 5-C7cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), WO 2022/096356 PCT/EP2021/079940 or h3c ch.
CH3z C h3 A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and is an integer in the range of 1 to 20 and the repeating units are the same or different, compound (A) of general formula (II) wherein x! and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, compound (A) of general formula (III) a o—c—& wherein is linear or branched, substituted or unsubstituted C3 to C20alkyl, 2is linear or branched, substituted or unsubstituted C! to C30 alkyl; and compound (A) of general formula (IV) WO 2022/096356 PCT/EP2021/079940 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted or unsubstituted C3 to C20 alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber; and (iii)at least one meta hydroxide.
In a preferred embodiment, A! is selected from linear or branched, substituted or unsubstituted C2-C8 alkylene and substituted or unsubstituted cyclohexylene, A2 is independently selected from H, linear or branched, substituted or unsubstituted C1-C8alkyl, C1-C12alkyloxy, substituted or unsubstituted cyclohexyl and cyclohexyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C1-C8alkyl or a group of the formula (a-1) or A3 and A4, together with the nitrogen atom to which they are bonded, form a morpholino group, and a is an integer in the range of 1 to 10.
In an embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), WO 2022/096356 PCT/EP2021/079940 wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c chN—A2(a-1) ch3z c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, (ii) at least one UV absorber; and(iii) at least one metal hydroxide.
In another embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (II), WO 2022/096356 PCT/EP2021/079940 x! wherein o—c—& x! and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, (ii) at least one UV absorber; and (iii)at least one meta hydroxide.
In another embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (III), compound (A) of general formula (III) wherein is linear or branched, substituted or unsubstituted C3 to C20alkyl, 2is linear or branched, substituted or unsubstituted C! to C30 alkyl; (ii) at least one UV absorber; and (iii)at least one meta hydroxide.
In another embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound WO 2022/096356 PCT/EP2021/079940 13 having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (IV), compound (A) of general formula (IV) (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted orunsubstituted C3 to C20alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8; (ii) at least one UV absorber; and(iii)at least one meta hydroxide.
In an embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof,compound (A) of general formula (I) WO 2022/096356 PCT/EP2021/079940 wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12cycloalkyloxy, 10A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c ch3N—A2(a-1) ch3z c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, compound (A) of general formula (II) (II) WO 2022/096356 PCT/EP2021/079940 wherein x!and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, and compound (A) of general formula (III) dll) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl;and (ii) at least one UV absorber; and(iii)at least one meta hydroxide.
In an embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) wherein WO 2022/096356 PCT/EP2021/079940 16 A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), CH3z C h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, compound (A) of general formula (II) (II) wherein x 7and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, and compound (A) of general formula (IV) WO 2022/096356 PCT/EP2021/079940 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted orunsubstituted C3 to C20alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8; (ii) at least one UV absorber; and(iii)at least one meta hydroxide.
In an embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) wherein WO 2022/096356 PCT/EP2021/079940 18 A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), CH3z C h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, compound (A) of general formula (III) (III) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl;and compound (A) of general formula (IV) WO 2022/096356 PCT/EP2021/079940 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted orunsubstituted C3 to C20alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8; (ii) at least one UV absorber; and(iii)at least one meta hydroxide.
In an embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) wherein WO 2022/096356 PCT/EP2021/079940 A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), CH3z C h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, and compound (A) of general formula (II) (II) wherein x 7and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy; (ii) at least one UV absorber; and(iii)at least one meta hydroxide.
In an embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having WO 2022/096356 PCT/EP2021/079940 21 a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof,compound (A) of general formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7 cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), a2 is independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, C!-C12 alkyloxy, substituted or unsubstituted C5-C12cycloalkyl and C5-C12cycloalkyloxy, A3and A4 are independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), H3Cx ch3(a-1) CH3 ch3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, and compound (A) of general formula (III) WO 2022/096356 PCT/EP2021/079940 dll) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl;and (ii) at least one UV absorber; and (iii)at least one meta hydroxide.
Compound A of general formula (I): In an embodiment, the stabilizer mixture comprises at least one compound (A) selected from general formula (I), general formula (II), genera formula (III), general formula (IV), and mixtures thereof.
In an embodiment, the stabilizer mixture comprises at least one compound (A) of genera formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, C!-C12 alkyloxy, substituted or unsubstituted C5-C12cycloalkyl and C5-C12cycloalkyloxy, WO 2022/096356 PCT/EP2021/079940 23 A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted 0!-012 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c ch, ch3 c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, Within the context of the present invention, the term alkyl, as used herein, refers to acyclic saturated aliphatic residues, including linear or branched alkyl residues.
As used herein, "branched" denotes a chain of atoms with one or more side chains attached to it. Branching occurs by the replacement of a substituent, e.g., a hydrogen atom, with a covalently bonded aliphatic moiety.
Representative examples of linear and branched, unsubstituted C!-C12 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2- ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n- heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-propy heptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, n-nonyl, n-decyl, n- undecyl, isoundecyl, 1-methylundecyl, n-dodecyl, isododecyl, and 1,1,3,3,5,5- hexamethylhexyl.
Representative examples of C!-C12 alkyloxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy.
In a preferred embodiment, alkyloxy is selected from methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy and octoxy. In a more preferred embodiment, alkyloxy is propoxy.
Representative examples of C5-C12 cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl.
Representative examples of C5-C12cycloalkyloxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclononyloxy, cyclodecyloxy, cycloundecyloxy, and cyclododecyloxy.
WO 2022/096356 PCT/EP2021/079940 24 In a preferred embodiment the cylcoalkyloxy is cyclohexoxy.
A preferred example of phenyl substituted by 1, 2 or 3 C1-C4alkyl is 2,4-dimethylphenyl.
Preferred C2-C18 alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene and hexamethylene. In a more preferred embodiment, alkylene is hexamethylene.
An example of C5-C7cycloalkylene is cyclohexylene.
An example of C1-C4alkylenedi(C 5-C7cycloalkylene) is methylenedicyclohexylene.
Examples of the radicals A3 and A4 together with the nitrogen atom to which they are bonded, forming a 5- to 10-membered heterocyclic ring, are 1-pyrrolidyl, piperidyl, morpholinyl, 1- piperazinyl, 4-methyl-l-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperaziny or 4,5,5,7-tetramethyl-l-homopiperazinyl, preferably morpholinyl.
In the compound (A) of the general formula (I) the terminal group attached to the diamino residue is for example hydrogen or a group of the formula A3-NA4 and the terminal group attached to the triazine radical is for example a group of the formula --------N----------A־!----------- N------ H CH3 H3C l^ J_CH3CH3 H3C־> In a preferred embodiment, A! is hexamethylene, and A2 is hydrogen, and propoxy.
In a preferred embodiment, A3 is butyl, , and WO 2022/096356 PCT/EP2021/079940 In a preferred embodiment, A4 is butyl.
In a preferred embodiment, a is an integer in the range of 1 to 10.
Compound A of general formula (II): In an embodiment, the stabilizer mixture comprises at least one compound (A) of genera formula (II) (ID wherein x!and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, In a preferred embodiment, x! and x 2 are independently selected from linear or branched, unsubstituted C! to C30 alkyloxy.
Representative examples of linear or branched, unsubstituted C! to C30 alkyloxy are methyloxy, ethyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy, henicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy and triacontyloxy.
In a preferred embodiment, x! and x 2 are each undecyloxy.
Compound (A) of general formula (III): In an embodiment, the stabilizer mixture comprises at least one compound (A) of genera formula (III) WO 2022/096356 PCT/EP2021/079940 dll) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl; In a preferred embodiment, Y! is linear or branched, unsubstituted C3 to C20alkyl.
In an embodiment, Y! is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl.
In a preferred embodiment, Y!is selected from propyl, and dodecyl.
In a preferred embodiment, Y2 is linear or branched, unsubstituted C! to C30alkyl.
In an embodiment, Y2 is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl.
In a preferred embodiment, Y2 is selected from pentadecyl, and heptadecyl.
Compound (A) of general formula (IV): In an embodiment, the stabilizer mixture comprises at least one compound (A) of genera formula (IV).
WO 2022/096356 PCT/EP2021/079940 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted or unsubstituted C3 to C20 alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and In a preferred embodiment, Y3 is selected from linear or branched, unsubstituted C3 to Calkyl and C3 to C20 alkylidene.
Representative examples of alkylidene having up to 20 carbon atoms are methylidene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, heptylidene, octylidene, nonylidene, decylidene, undecylidene, dodecylidene, tridecylidene, tetradecylidene, pentadecylidene, hexadecylidene, heptadecylidene, octadecylidene, nonadecylidene, and icosylidene.
In a preferred embodiment, Y!is selected from decyl.
In a preferred embodiment, Y3 is selected from decyl, and nonylidene.
In a preferred embodiment, the stabilizer mixture comprises: (i) at least one compound (A) selected from general formula (I), wherein A! is selected from C2-C18alkylene, C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7cyclo alkylene), A2 is independently selected from C1-C12 alkyloxy, and C5-C12cycloalkyloxy, A3 and A4 is independently selected from H, C1-C12 alkyl, C5-C12 cycloalkyl and a group of the formula (a-1), or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and a is an integer in the range of 1 to 20 and the repeating units are the same or different, WO 2022/096356 PCT/EP2021/079940 28 general formula (II), general formula (III), general formula (IV), and mixtures thereof; (ii) at least one UV absorber; and (ill) at least one metal hydroxide.
In another preferred embodiment, the stabilizer mixture comprises: (i) at least one compound (A) selected from general formula (I), wherein A! is selected from C2-C18 alkylene, C5-C7 cycloalkylene, and C!-C4 alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, C1-C12 alkyl, and C5-C12cycloalkyl, A3 and A4 is independently selected from H, 0012-ן alkyl, C5-C12 cycloalkyl and a group of the formula (a-1), or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units are the same or different, general formula (II), general formula (III), general formula (IV), and mixtures thereof; (ii) at least one UV absorber; and (iii) at least one metal hydroxide.
In a preferred embodiment, the compound (A) is at least one compound selected from the formula (A-1), (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), and (A-8) (A-1), (A-2), WO 2022/096356 PCT/EP2021/079940 N----- C4Hg C4Hg (A-3) c4h9 N I >ף ן/ — N—C4H8 wherein a is an integer in the range of 1 to 10, (A-4), (A-5) WO 2022/096356 PCT/EP2021/079940 (A-6) (A-7), and (A-8) wherein n is 2.
WO 2022/096356 PCT/EP2021/079940 31 In a more preferred embodiment, the compound (A) is at least one compound selected from the formula (A-l), (A-3), (A-4), (A-5), (A-6), (A-7), and (A-8).
In another preferred embodiment, the compound (A) is a compound of formula (A-9) (A-9) 5 wherein a is an integer in the range of 1 to 10.
Organic Material In an embodiment, the organic materia is selected from: 1. Polymers of monoolefins and diolefins, for example polyethylene, polypropylene, polyisobutylene, polybut-l-ene, poly-4-methylpent-l-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, (which optionally can be crosslinked), for example high density polyethylene (HOPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe- rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated. These metal complexes may be in the free form or a form fixed on substrates, typically on substrates such as activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation WO 2022/096356 PCT/EP2021/079940 32 medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or Illa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE). 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-l-ene copolymers, propylene/isobutylene copolymers, ethylene/but-l-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-olefin is gene- rated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alky methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides. 4. Hydrocarbon resins (for example C5-Cg) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.) - 4.) may have any stereo structure including syndic- tactic, isotactic, hemi-isotactic or atactic; where polymers atactic stereostructure are preferred. Stereoblock polymers are also included.
. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene). 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, a-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including WO 2022/096356 PCT/EP2021/079940 33 syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Ste- reoblock polymers are also included. 6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selec- ted from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, viny acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene. 6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH). 6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
Homopolymers and copolymers may have any stereostructure including syndiotactic, isotac- tic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included. 7. Graft copolymers of vinyl aromatic monomers such as styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers. 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
WO 2022/096356 PCT/EP2021/079940 34 9. Polymers derived from a , P -unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
. Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers, for example acrylonitrile/ butadiene copolymers, acryIonitrile/aIky acrylate copolymers, acryIonitrile/aIkoxyaIkyI acrylate or acrylonitrile/vinyl halide copolymers or aery- lonitrile/ alkyl methacrylate/butadiene terpolymers. 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above. 12. Homo polymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers. 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof. 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an ela- stomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). 17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydan- toins and polybenzimidazoles. 18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones or lactides, for example polyethylene terephthalate, polybuty- WO 2022/096356 PCT/EP2021/079940 lene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoates as well as copolyether esters derived from hydroxyl-terminated polyethers, and also polyesters modified with polycarbonates or MBS. Copolyesters may comprise, for example - but are not limited to - polybutylenesuccinate/terephtalate, polybuty- I eneadipate/tere phthalate, polytetra methyleneadipate/terephthalate,polybutylensuccinate/adipate, poly butylensuccinate/car donate, poly-3-hydroxybutyrate/octa noate copolymer, poly-3-hydroxybutyrate/hexanoate/deca noate terpolymer. Furthermore, aliphatic polyesters may comprise, for example - but are not limited to - the class of poly(hydroxyalkanoates), in particular, poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylenesuccinate, polypropylenesuccinate, poly butylenesuccinate,polyhexamethylenesuccinate, polyethyleneadipate, polypropyleneadipate, polybutyleneadi- pate, polyhexamethyleneadipate, polyethyleneoxalate, polypropyleneoxalate, polybutylene- oxalate, polyhexamethyleneoxalate, polyethylenesebacate, polypropylenesebacate, polybu- tylenesebacate and polylactic acid (PLA) as well as corresponding polyesters modified with polycarbonates or MBS. The term "polylactic acid (PLA)" designates a homo-polymer of pre- ferably poly-L-lactide and any of its blends or alloys with other polymers; a co-polymer of lactic acid or lactide with other monomers, such as hydroxy-carboxylic acids, like for example glycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydr- oxy-valeric acid, 6-hydroxy-caproic acid and cyclic forms thereof; the terms "lactic acid" or "lactide" include L-lactic acid, D-lactic acid, mixtures and dimers thereof, i.e. L-lactide, D- lactide, meso-lactide and any mixtures thereof. 19. Polycarbonates and polyester carbonates.
. Polyketones. 21. Polysulfones, polyether sulfones and polyether ketones. 22. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde re- sins and melamine/formaldehyde resins. 23. Drying and non-drying alkyd resins. 24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy aery- lates, urethane acrylates or polyester acrylates. 26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
WO 2022/096356 PCT/EP2021/079940 36 27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators. 28. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives. 29. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
. Naturally occurring and synthetic organic materials which are pure monomeric com- pounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials. 31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carbo- xylated styrene/butadiene copolymers.
In a preferred embodiment, the organic material is selected from linear low-density polyethylene, low-density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer, polypropylene homopolymer and polypropylene copolymer.
In a more preferred embodiment, the organic material is low-density polyethylene.
Chlorine containing compound In an embodiment, the presently claimed invention is directed to a method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm.
The chlorine containing compound can be an agrochemical compound or a bleaching agent.
The agrochemical compound can be an insecticide, fungicide, nematicide, and mixtures thereof.
The agrochemical compound is selected from pyrethroid, dicarboximide, CICH2-CH=CHCI, Cl3C-NO2, pyrethroid, phthalimide, benzoylurea, imidazole, and mixtures thereof.
WO 2022/096356 PCT/EP2021/079940 37 The agrochemical compound is selected from permethrin, procymidone, 1,3-dichloropropene, chloropicrin, y-cyhalothrin, captan, teflubenzuron, prochloraz, and mixtures thereof.
The bleaching agent is sodium hypochlorite, chlorine dioxide, and chloramines, preferably sodium hypochlorite.
UV Absorber In an embodiment, the stabilizer mixture comprises at least one UV absorber.
In an embodiment, the at least one UV absorber is selected from 2-(2'- hydroxyphenyl)benzotriazoles, 2-hydroxy benzophenones, 2-(2-hydroxy phenyl) -1,3,5-triazines and mixtures thereof.
In an embodiment, the 2-(2'-hydroxyphenyl)benzotriazole is selected from 2-(2H- Benzotriazol-2-yl)-4,6-bis(l-methy 1-1-phenyl ethyl) phenol, 2-(2'-hydroxy-5'-methyl phenyl)- benzotriazole, 2 - (3', 5'-di-tert-butyl -2'-hydroxy phenyl) benzotriazo Ie, 2-(5'-tert-butyl-2'- hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'- (1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2 - (3', 5'-di-tert-butyl -2'-hydroxy phenyl) -5-ch loro-benzotriazol e,2-(3'-tert-buty I-2'-hydroxy-5'-methyl phenyl) -5-ch loro-benzotriazole, 2-(3'-sec-buty I-5'-tert-butyl -2'-hydroxy phenyl) benzotriazo Ie, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2 - (3', 5'-di-tert-amyl -2'-hydroxy phenyl) benzotriazo Ie, 2-(3',5'- bis-( a , a -di methyl benzyl) -2'-hydroxy phenyl )benzotriazo Ie, 2-(3'-tert-butyl -2'-hydroxy-5'- (2- octyl oxycar bony I ethyl) phenyl) -5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)-carbonylethyl]-2'-hydroxypheny I)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-methoxycarbonyl ethyl) phenyl)-5-ch loro-benzotriazo Ie, 2-(3'-tert-butyl -2'-hydroxy-5'- (2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl -2'-hydroxy-5'- (2-octyl oxycarbonyl ethyl) phenyl) benzotriazo Ie, 2-(3'-tert-butyl-5'-[2-(2-ethyl hexyl oxy) car bony I ethyl] -2'-hydroxy phenyl) benzotriazole, 2-(3'-dod ecyl -2'-hydroxy-5'- methyl phenyl) benzotriazole, 2-(3'-tert-butyl -2'-hydroxy-5'- (2-isooctyl oxycar bony I ethyl) phenyl benzotriazole, 2,2'-methylene-bis [4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert- bu ty I-5'-(2-meth oxyca r bony I ethyl) -2'-hydroxy phenyl] -2 H-benzotriazole with polyethylene glycol 300; [r—CH2CH2—COO-CH2CH29־— , where R = 3'-tert-butyl-4'-hydroxy-5'-2H- benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a , a -dimethylbenzyl)-5'-(l,l,3,3-tetramethylbutyI)-phenyl]benzotriazole; and 2-[2'-hydroxy-3'- (1,1,3,3-tetra methyl buty I)-5'-( a , a -dimethylbenzyl)-phenyl]benzotriazole, and mixtures thereof.
In a preferred embodiment, the 2-(2'-hydroxyphenyl)benzotriazole is 2-(2'-hydroxy-5'- (1,1,3,3-tetra methyl buty I) phenyl) benzotriazole.
WO 2022/096356 PCT/EP2021/079940 38 In an embodiment, the 2-hydroxybenzophenone is selected from 4-hydroxy, 4-methoxy, 4- octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivatives and mixtures thereof.
In an embodiment, the 2-(2-hydroxyphenyl)-l,3,5-triazine is selected from 2,4,6-tris(2- hyd roxy-4-octyloxypheny I)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-di methyl phenyl) -1,3,5-triazine, 2-(2,4-d ihyd roxypheny l)-4,6-bis(2,4-d i methyl phenyl) -1,3,5-triazine, 2,4-bis(2 - hydroxy-4-propyloxy phenyl) -6-(2,4-d imethy I pheny I)-1,3,5-triazi ne, 2-(2- hyd roxy-4-octyloxypheny I)-4,6-bis(4-methyl phenyl)-1,3,5-triazi ne, 2-(2-hydroxy-4-dodecyloxy pheny I)-4,6-bis (2,4-d imethy I pheny I)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyl oxy pheny I)-4,6-bis (2,4-d imethy I pheny I)-1,3,5-triazi ne, 2-[2-hydroxy-4- (2-hydroxy-3- bu tyloxy propoxy) pheny I]-4,6-bis(2,4-d imethy I)-1,3,5-triazi ne, 2-[2-hydroxy-4-(2-hydroxy-3- octyl oxy propyl oxy) pheny I]-4,6-bis (2,4-d imethy I)-1,3,5-triazine, 2-[4-(dod ecy I oxy/t ridecy loxy-2-hydroxy pro poxy) -2-hyd roxypheny I]-4,6-bis(2,4-d imethy I pheny I)- 1,3,5-triazi ne, 2-[2-hydroxy-4- (2-hydroxy-3-dodecyl oxy pro poxy) pheny I]-4,6-bis (2,4-di methyl pheny I)-1,3,5-triazine, 2 - (2 - hyd roxy-4-hexyl oxy) pheny I-4,6-di pheny I-1,3,5-triazi ne, 2-(2-hyd roxy-4-methoxy pheny I)-4,6-di pheny I-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy pro poxy) pheny I]-1,3,5-triazine, 2-(2-hyd roxypheny I)-4-(4-methoxy phenyl)- 6-pheny I-1,3,5-triazi ne, 2-{2-hydroxy-4-[3-(2-ethylhexyl-l-oxy)-2-hyd roxypropyl oxy] pheny I]-4,6-bis(2,4-d imethy I pheny I)-1,3,5-triazi ne, 2,4-bis(4-[2-ethy I hexyl oxy]-2-hyd roxypheny I)-6-(4-methoxy phenyl)-1,3,5-triazi ne, 2,4-bis (4-bi phenylyl)- 6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl] -1,3,5-triazine, Dodecanedioic acid, l,12-bis[2-[4- (4,6-diphenyl-l,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl]ester and mixtures thereof.
In a preferred embodiment, the 2-(2-hydroxyphenyl)-l,3,5-triazine is 2,4-bis(4-biphenylyl)-6- [2-hydroxy-4- (2-ethylhexyloxy)phenyl] -1,3,5-triazine.
Metal hydroxide In an embodiment, the stabilizer mixture comprises at least one metal hydroxide.
In an embodiment, the at least one metal hydroxide is selected from the group consisting of hydrotalcite, and magnesium hydroxide.
Hydrotalcite In a preferred embodiment, the hydrotalcite is a mixed hydroxide of the formula (Z-l) or (Z- II).
M2+1_gM3+g(OH)2(Ab-)g/b x c H2O (Z-l) M2+dAI3%(OH،eb(Ab )exf H20 (Z-ll) M2+ is selected from Ca 2+, Mg2+, Sr 2+, Ba 2+, Zn 2+, Pb2+, Sn 2+ and Ni2+.
WO 2022/096356 PCT/EP2021/079940 39 M3+ is selected from Al3+, B3+ and Bi3+. g is a number up to 0.5.
A׳' is an anion of valency b, selected from Ch, Br, NO3, CO32h SO/ or SeO42 b is an integer from 1 to 4. c is zero, 1 or 2. d is a number up to 6. e is a number up to 2. f is zero or a number up to 15.
In a more preferred embodiment, hydrotalcites are layered double hydroxides that contain positively charged hydroxide layers and charge balancing anions located in the interlayer region.
In an even more preferred embodiment, hydrotalcite is at least one magnesium aluminum hydroxide carbonate hydrate which is for example commercially available as Hycite®713, ‘DHT-4A, ‘DHT-4V, ‘DHT-4A-2, ‘DHT-40 or Sorbacid®911, or zinc aluminum hydroxide carbonate hydrate which is for example commercially available as aZHT-4V or Sorbacid®944, or mixtures thereof.
In a most preferred embodiment, hydrotalcite is a magnesium aluminum hydroxide carbonate hydrate which is for example commercially available as Hycite a713 or DHT-4A.
In another aspect, the presently claimed invention is directed to a stabilizer mixture comprising: (i) at least one compound (A) selected from the general formula (A-l), genera formula (A-2), genera formula (A-4), general formula (A-5), general formula (A-6), general formula (A-7), and general formula (A-8); (ii) at least one UV absorber; and (iii)at least one metal hydroxide.
In a preferred embodiment, the stabilizer mixture comprises: (i) at least one compound (A) selected from the general formula (A-l), genera formula (A-4), genera formula (A-5), general formula (A-6), general formula (A-7), and general formula (A-8); (ii) at least one UV absorber; and (iii)at least one metal hydroxide.
WO 2022/096356 PCT/EP2021/079940 In an embodiment, the weight ratio of the at least one compound (A) to the at least one UV absorber is in the range of 1:1 to 20:1, preferably is in the range of 5:1 to 15:1, more preferably is in the range of 9:1 to 13:1, and most preferably is in the range of 11.7:1.
In an embodiment, the weight ratio of the at least one compound (A) to the at least one meta hydroxide is in the range of 1:10 to 10:1, preferably is in the range of 1:5 to 5:1, more preferably is in the range of 1:3 to 3:1, and most preferably is in the range of 2.5:1.
In an embodiment, the weight ratio of the at least one UV absorber to the at least one hydroxide is in the range of 10:1 to 1:20, preferably is in the range of 5:1 to 1:15, more preferably is in the range of 3:1 to 1: 10, and most preferably is in the range of 1:4.7.
Light stabilizer: In an embodiment, the stabilizer mixture further comprises at least one light stabilizer.
In an embodiment, the light stabilizer is selected from bis(2,2,6,6-tetramethyl-4- piperidyI)sebacate, bis(2,2,6,6-tetramethyl-4-pi peridyI)succinate, bis(l,2,2,6,6-pentamethyl- 4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl -4-piperidyl)sebacate, bis(1,2,2,6,6- pen tarn ethyl -4-pi peridy I) n- butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, thecondensate of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-tert-octy lamino-2,6-dich loro-1, 3,5-triazine,tris (2,2,6,6-tetramethy 1-4-piperidyl) nitrilotriacetate, tetra kis (2,2,6,6-tetra methyl -4-pi peridy I)-1,2,3,4-butanetetracarboxy I ate, 1,1'-(1,2-ethanediyl)-bis (3,3,5,5-tetrame-thyl pi perazino ne), 4-benzoy I-2,2,6,6-tetra methyl pi peridi ne, 4-stearyloxy-2,2,6,6-tetram ethyl pi peridi ne, bis(l,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di- tert-butyl benzyl) ma Ion ate, 3-n-octyl-7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4- dione, bis(l-octyloxy-2,2,6,6-tetra methyl pi peridy I)sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl- 4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-l, 3,5-triazine, the condensate of 2-chIoro-4, 6-bis(4-n-butylamino-2,2,6,6-tetramethyl piperidyI) -1,3,5-triazine and l,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n- butylamino- 1,2,2,6,6-penta methyl pi peridy I)-1,3,5-triazine and l,2-bis(3-a mi no propyl ami no) ethane, 8-acety I-3-dodecyl -7,7,9,9-tetra methyl -1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecy I-l-(2,2,6,6-tetra methyl -4-pi peridy I) pyrrolidine- 2,5-dione, 3-dodecyl-l-(l,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N'- bis(2,2,6,6-tetra methy I-4-pi peridy I) hexa methylenediamine and 4-cyc 10 hexyl a mi no-2, 6- dichloro-1, 3,5-triazine, a condensate of l,2-bis(3-aminopropylamino)ethane and 2,4,6- trichloro-1, 3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine; N-(2,2,6,6- WO 2022/096356 PCT/EP2021/079940 41 tetram ethy I-4-pi peridy I)-n-dodecyl succinimide, N-(l,2,2,6,6-pentamethyl-4-piperidyl)-n- dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-l-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospiro- [4,5]decane and epichlorohydrin, l,l-bis(l,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2- (4-meth oxy phenyl) ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with l,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl- 4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-a-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or l,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4- bis[N-(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-l,3,5-triazine, 5 -(2-ethy I hexanoy I) oxy methyl -3,3,5-tri methyl -2-morpholinone, Sanduvor, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, the reaction product of 2,4-bis[(l-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s- triazine with N,N’-bis(3-aminopropyl)ethylenediamine), l,3,5-tris(N-cyclohexyl-N-(2,2,6,6- tetramethylpiperazine-3-one-4-yl)amino)-s-triazine, l,3,5-tris(N-cyclohexyl-N-(l,2,2,6,6- pentamethylpiperazine-3-one-4-yl)amino)-s-triazine, and mixtures thereof.
In a preferred embodiment, the light stabilizer is condensate of l-(2-hydroxyethyl)-2,2,6,6- tetramethyl-4-hydroxypiperidine and succinic acid.
In another aspect, the presently claimed invention is directed to a composition comprising: I. an organic material, and II. a stabilizer mixture as defined above.
In an embodiment, the weight ratio of the organic material to the stabilizer mixture is in the range of 0.005:10%, preferably 0.005:5 %, more preferably 0.01:2.5 %, and most preferably 0.05:2 %, relative to the weight of the organic material.
The individual components of the present stabilizer mixture may be added to the organic material to be stabilized either individually or mixed with one another. They can be added to a polymer before, during or after the polymerization or before or after the crosslinking.
The composition according to the present invention or its individual components can be incorporated into the organic materia to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed stabilizer to the organic material, if necessary, with subsequent evaporation of the solvent. The stabilizers can be added to the organic material in the form of a powder, granules or a masterbatch, which contains said stabilizers in, for example, a concentration of from 2.5 to 90%, preferably 2.5 to 25%, by weight.
WO 2022/096356 PCT/EP2021/079940 42 Examples of processing or transformation of the materials stabilized according to the present invention are: Injection blow molding, extrusion, blow molding, rotomolding, in mold decoration (back injection), slush molding, injection molding, co-injection molding, forming, compression molding, pressing, film extrusion (cast film; blown film), fiber spinning (woven, non-woven), drawing (uniaxial, biaxial), annealing, deep drawing, calandering, mechanical transformation, sintering, coextrusion, coating, lamination, crosslinking (radiation, peroxide, silane), vapor deposition, weld together, glue, vulkanization, thermoforming, pipe extrusion, profile extrusion, sheet extrusion; sheet casting, spin coating, strapping, foaming, recycling / rework, extrusion coating, visbreaking (peroxide, thermal), fibre melt blown, spun bonded, surface treatment (corona discharge, flame, plasma), sterilization (by gamma rays, electron beams), cast polymerization (R&M process, RAM extrusion), gel-coating, tape extrusion, GMT- process, SMC-process, plastisol, and dipping (PVC, latex).
Additive (A) In an embodiment, the composition further comprising at least one additive (A) selected from antioxidants, UV absorber, slip agents, anti-block agents, thermal fillers, pigments, anti-fog agents, anti-mist agents and additional additives (B). 1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di- tert-butyl-4-isobuty I phenol, 2,6-dicyclopenty I-4-methyl phenol, 2-( a - methyl cyclohexyl) -4,6- dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl- 4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(l'-methylundec-l'-yl)phenol, 2,4- dimethyl-6-(l'-methylheptadec-l'-y I) phenol, 2,4-d i methy I-6-(1'-methyl tridec-l'-y I) ph eno and mixtures thereof. 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methy I phenol, 2,4-dioctylthiomethyl-6-ethyl phenol, 2,6-di-dodecylthiomethyl -4-nonyl ph eno I. 1.3. Hydroquinones and alkylated hydroquinones , for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxypheny stearate, bis(3,5-di-tert-butyl-4- hydroxyphenyl) adipate. 1.4. Tocopherols , for example a-tocopherol, /3-tocopherol, y-tocopherol, 5-tocopherol and mixtures thereof (vitamin E).
WO 2022/096356 PCT/EP2021/079940 43 1.5. Hydroxylated thiodiphenyl ethers , for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl -3-methyl phen 01), 4,4'-thiobis(6-tert- butyl-2-methyl phen 01), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4- hydroxy phenyl) disulfide. 1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( a - methylcyclo hexyl) phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'- methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'- ethy I idenebis(4,6-di-tert-buty I phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2'-methylenebis[6-( a - methyl benzyl) -4-nonyl phen 01], 2,2'-methylenebis[6-( a , ct -di methyl benzyl) -4-nonyl phen 01], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'- m ethy Ie nebis(6-tert-butyl -2-methyl phen 01), 1,1-bis (5-tert-butyl -4-hydroxy-2-methyl phenyl) butane, 2,6-bis (3-tert-butyl -5-methyl -2 -hydroxy benzyl) -4-methyl phen 01,1,1,3-tris (5-tert-butyl -4-hydroxy-2-methyl phenyl) butane, 1,1-bis(5-tert-butyl-4-hydroxy-2- methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'- hydroxypheny I) butyrate], bis (3-tert-buty I-4-hydroxy-5- met hyl -phenyl) dicyclopentadiene,bis[2-(3'-tert-butyI -2'-hydroxy-5'-methyl benzy I)-6-tert-buty I-4-methyl phenyl]terephthalate, 1,1-bis-(3,5-di methyl -2-hydroxy phenyl) butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe-nyl) propane, 2,2 - bis(5-tert-buty I-4-hyd roxy2 - m ethy I ph eny I)-4-n-dodecyl mercapto butane, 1,1,5,5-tetra-(5-tert-buty I-4-hydroxy-2-methyl phenyl) penta ne. 1.7. 0-, N- and S-benzyl compounds , for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-buty I benzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hyd roxybenzyl)a mine, bis(4- tert-buty I-3-hydroxy-2,6-di methyl benzy I) dithioterephthalate, bis(3,5-di-tert-butyl-4-hyd roxybenzyl) sulfide, isooctyl-3,5-di-tert-buty I-4-hydroxy benzy I mercaptoacetate. 1.8. Hydroxybenzylated malonates , for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- d roxybenzyl) ma Ion ate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecyl mercaptoethyl -2,2-bis (3,5-di-tert-butyl -4-hydroxy benzy I) ma Ion ate, bis[4-(l,l,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate. 1.9. Aromatic hydroxybenzyl compounds, for example l,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-tri methyl benzene, l,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thyl benzene, 2,4,6-tris (3,5-di-tert-buty I-4-hydroxy benzy I) pheno I. 1.10. Triazine compounds , for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hyd roxyani lino)- 1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-l,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-l,2,3-triazine, 1,3,5-tris (3,5-di-tert-buty I-4- hydroxy benzy I) isocyan urate, 1,3,5-tris (4-tert-buty I-3-hydroxy-2, 6- WO 2022/096356 PCT/EP2021/079940 44 dimethyl benzyl) isocyan urate, 2,4,6-tris(3,5-d i-tert-buty I -4-hydroxy phenylethyl) -1,3,5-triazine, 1,3,5-tris(3,5-d i-tert-buty 1-4-hydroxy phenyl propionyl)-hexahydro-1, 3,5-triazine,1,3,5-tris (3,5-dicyclo hexyl -4-hydroxy benzyl) isocyanurate. 1.11. Benzylphosphonates , for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diet hyl -3,5-di-tert-buty I-4-hydroxy benzyl phosphonate, dioctadecyl3,5-di-tert-butyl-4- hydroxybenzyI phosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4- hydroxybenzylphosphonic acid. 1.12. Acylaminophenols , for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-d i-tert-buty I-4-hydroxy phenyl) carbamate. 1.13. Esters of 3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or p01yhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylol pro pa ne, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.14. Esters of 3 -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylol pro pa ne, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis [2- {3-(3-tert-buty 1-4-hydroxy-5-methyl phenyl) propionyloxy}-l,l-dimethylethy I]-2,4,8,10- tetraoxaspiro [5.5] undeca ne. 1.15. Esters of 3 -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylol pro pa ne, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.16. Esters of 3,5-di-tert-butyl-4-hydroxypheny acetic acid with mono- or polyhydric alco- hols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylol pro pa ne, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
WO 2022/096356 PCT/EP2021/079940 45 1.17. Amides of /3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for example N,N'- bis(3,5-di-tert-buty I-4-hydroxy phenyl propionyl) hexamethylenediamide, N,N'-bis (3,5-di-tert- butyl-4-hydroxy phenyl propionyl) tri methylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl propionyl) hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard®XL-l, supplied by Uniroyal). 1.18. Ascorbic acid (vitamin C) 1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec- butyl-p-phenylenediamine, N,N'-bis(l,4-dimethyl pentyl) -p-phenylenediami ne, N,N'-bis(l- ethy I-3 - methy I penty I)-p-phenylenediamine, N,N'-bis(l- methyl hepty I)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N '-di phenyl -p-phenylenediami ne, N,N'-bis(2- naphthyl)-p-phenylenediami ne, N - isopro py I-N'-phenyl -p-phenylenediami ne, N-(l,3-di methyl butyl)-N'-phenyl-p-phenylenediamine, N-(l-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cycl ohexy I -N'-phenyl -p-phenylenediami ne, 4-(p-toluenesulfamoyl) di phenyl a mi ne, N,N'-di methy I-N,N'-di-sec-butyl-p-phenylenediamine,diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1- naphthylamine, N-(4-tert-octyl phenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadeca noy I am inop hen 01, bis (4-methoxy phenyl)amine, 2,6-d i-tert-butyl-4-di methyl a mi no- methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra- m ethy I-4,4'-diami nodiphenyl methane, l,2-bis[(2-methylphenyl)amino] ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(r,3'-dimethylbutyl)phenyl]amine, tert- octylated N-phenyl-l-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert- octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert- butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-l,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-l,4- diaminobut-2-ene. 2. UV absorbers and light stabilizers The composition may comprise UV absorbers, in addition to those disclosed above. 2.1. Esters of substituted and unsubstituted benzoic acids , for example 4-tert-butyl-pheny salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4- hydroxy benzoate, 2-methy I-4,6-di-tert-butyl phenyl 3,5-di-tert-butyl -4-hydroxy benzoate.
WO 2022/096356 PCT/EP2021/079940 46 2.2. Acrylates , for example ethyl a -cyano-/? ,3 -diphenylacrylate, isooctyl a -cyano- 3,3 ־ diphenylacrylate, methyl a-carbomethoxycinnamate, methyl a -cyano- 3 -methyl-p- methoxycinnamate, butyl a-cyano-/3-methyl-p-methoxy-cinnamate, methyl a- carbomethoxy-p-methoxycinnamate, N-(/3 -carbomethoxy-/3 -cyanovinyl)-2-methylindoline, neopentyl tetra( a -cyano- 3 -3 -di phenyl aery I ate. 2.3. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(l,l,3,3-tetramethyl- butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalky esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, with or with- out additional ligands. 2.4. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani- Iide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of 0- and p-methoxy- disubstituted oxanilides and mixtures of 0- and p-ethoxy-disubstituted oxanilides.
Additive (B) 3. Metal deactivators , for example N,N'-diphenyloxamide, N-salicylal-N ’-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl propionyl) hydrazine, 3-salicyloylamino-l,2,4-triazole, bis(benzylidene)oxaly dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'- diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'- bis (sa I icy I oy I) th io p ro piony I di hydrazide. 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos- phite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecy pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4- di-cumyl phenyl) pentaerythritol di ph os phite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythrito diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4- di-tert-butyl -6-methyl phenyl) pentaerythritol di phosph Ite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert- butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H- d i be nz[d,g]- 1,3,2-dioxa phosphocin, bis (2,4-di-tert-butyl -6-methyl phenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fIuoro-2, 4,8,10-tetra-tert-butyl -12- methyl-dibenz[d,g]-l,3,2-dioxaphosphocin, 2,2', 2"-nitri 10 [triethyl tris (3,3', 5,5'-tetra-tert-buty I-1,1'-bi phenyl -2,2'-diyI) phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl- WO 2022/096356 PCT/EP2021/079940 47 2,2'-diy I) phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-l,3,2-dioxaphosphirane, phosphorous acid, mixed 2,4-bis(l,l-dimethylpropyl)phenyl and 4-(l,l-dimethylpropyl) phenyl triesters (CAS: 939402-02-5)., phosphorous acid, triphenyl ester, polymer with a- hydro-cu-hydroxypoly[oxy(methyl-l,2-ethanediyl)], C10-16-alkyl esters (CAS: 1227937-46- 3).
The following phosphites are especially preferred: Tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, (D) WO 2022/096356 PCT/EP2021/079940 O^ /^0x(F) O-P Y P-O-C18H37(G) . Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- di hexadecyl hydroxy la mi ne, N,N-dioctadecyl hydroxy I ami ne, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. 6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecy I nitrone,tridecyl n nitrone, N-hexadecyl-alpha-pentadecyl nitrone,heptadecyl nitro ne, N-hexadecyl-a Ip ha-heptadecyl nit rone,pentadecyl nitro ne, N-heptadecyl-alpha-heptadecyl nitrone, N-tetradecyl-alpha-N-octadecyl-alpha-N-ocatadecyl-alpha-N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. 7. Thiosynergists , for example dilauryl thiodipropionate, dimistryl thiodipropionate, disteary thiodipropionate or distearyl disulfide. 8. Peroxide scavengers , for example esters of (3 -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(b- dodecyl mercapto) pro pion ate. 9. Polyamide stabilizers , for example copper salts in combination with iodides and/or phos- phorus compounds and salts of divalent manganese.
. Basic co-stabilizers , for example melamine, polyvinylpyrrolidone, dicyandiamide, trially cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. 11. Nucleating agents , for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the WO 2022/096356 PCT/EP2021/079940 49 salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are l,3:2,4-bis(3’,4’-dimethylbenzylidene)sorbitol, 1,3:2,4- di (pa ram ethyldi benzyl ide ne) sorbitol, and 1,3:2,4-di (benzyl ide ne) sorbitol. 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, surface treated silica (as described e.g. in US-A-2007/60,697 and US-A-2009/111,918), glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, synthetic fibres. 13. Other additives , for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents. 14. Benzofuranones and indolinones , for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 3-[4-(2- acetoxyethoxy) phenyl] -5,7-di-tert-butyl benzofuran -2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy) phenyl] benzofuran -2-one, 3,3'-bis [5,7-di-tert-butyl -3-(4-[2-hydroxyethoxy] phenyl) benzofuran -2-one], 5,7-d I-te rt-bu ty I-3 -(4-ethoxy phenyl) benzofuran- 2-0 ne, 3-(4-acetoxy-3,5-di methyl phenyl) -5,7-di-tert-butyl benzofuran -2-one, 3-(3,5-di methyl -4-pivaloyloxy phenyl) -5,7-di-tert-butyl benzofuran -2-one, 3-(3,4-di methyl phenyl)- 5,7-di-tert-butyl benzofuran -2-0 ne, 3-(2,3-di methyl phenyl) -5,7-di-tert-butyl benzofuran -2- one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.
In another aspect, the presently claimed invention is directed to an article comprising the composition as described above.
In an embodiment, the article is a monolayer film or a multilayer film of three to twelve layers, having a total thickness of 100 to 300 microns, preferably 120 to 220 microns, more preferably 150 to 180 microns, most preferably 160 microns.
The multilayer film contains at least one compound (A) in at east one layer, and at least one compound of the UV absorber and a compound of the at least one metal hydroxide independently in another layers.
Such a multilayer film is typically made of three, five, seven, nine or eleven layers. This can lead to a film structure like (A-3)-(B-l)-(B-2)-(C-l)-(C-2), (A-3)-(B-l)-(B-2)-(C-l)-(C-3), (A- 3)-(B-3)-(A-2)-(B-l)-(B-2)-(C-l)-(C-2), and (A-3)-(B-3)-(A-4)-(B-l)-(B-2)-(C-l)-(C-2). Compounds such as (A-3), (B-3), (A-4), (B-l), (B-2), (C-l), and (C-2) are described in the examples.
WO 2022/096356 PCT/EP2021/079940 50 However, adjacent layers can also be coupled so that the final film article can be made of an even number of layers, i.e. two, four, six, eight, ten or twelve layers such as (A-3)-(B-l)-(B- 2)-(C-l), (A-3)-(B-l)-(B-2)-(C-2), and (A-3)-(B-l)-(B-2)-(C-2) and the like.
In a preferred embodiment, the article is a greenhouse film cover, mulch film, artificial turfs, or geomembrane.
In a more preferred embodiment, the greenhouse film cover, mulch film, artificial turf, or geomembrane is in contact with an agrochemical compound or bleaching agent.
In another aspect, the present invention is directed to a use of the stabilizer mixture for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having the chlorine content in the range of 100 to 600 ppm.
In an embodiment, the stabilizer mixture is used for stabilizing an organic material by reducing degradation induced by light, heat, or oxidation.
The organic materials stabilized according to this invention is used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties.
In more detail, the organic materials stabilized according to the present invention may be used for the preparation of the following devices: 1-1) Automotive applications, in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter / filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners / fixings, front end module, glass, hinges, lock systems, luggage / roof racks, pressed/stamped parts, seals, side impact protection, sound deadener / insulator and sunroof. 1-2) Devices for plane, railway, motor car (car, motorbike) including furnishings. 1-3) Devices for space applications, in particular rockets and satellites, e.g. reentry shields. 1-4) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters. 11-1) Electric appliances, in particular washing machines, tumblers, ovens (microwave oven), dishwashers, mixers, and irons. 11-2) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulating of electronics, semi-conductors, coffee machines, and vacuum cleaners.
WO 2022/096356 PCT/EP2021/079940 51 lll-l) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles, and knobs.
III-2) Rotor blades, ventilators and windmil vanes, solar devices, swimming pools, swimming poo covers, poo liners, pond liners, closets, wardrobes, dividing walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves, and conveyor belts.
III-3) Profiles of any geometry (window panes) and siding.
III-4) Glass substitutes, in particular extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.
III-5) Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
III-6) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles, and tarpaulins.
IV-1) Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
V-l) Plastic films in general (packaging, dump, laminating, swimming pools covers, waste bags, wallpaper, stretch and shrink wrap, raffia, desalination film, batteries, and connectors).
V -2) Agricultural films (greenhouse covers, tunnel, mulch, silage, bale wrap), especially in presence of intensive application of agrochemicals having high chlorine content.
V l-l) Food packing and wrapping (flexible and solid), BOPP, BOPET, bottles.
V I-2) Cartridges, syringes, medical applications, containers for any transportation, waste baskets and waste bins, waste bags, bins, dust bins, bin liners, wheely bins, container in general, tanks for water / used water / chemistry / gas / oil / gasoline / diesel; tank liners, boxes, crates, battery cases, troughs, medical devices such as piston, ophthalmic applications, diagnostic devices, and packing for pharmaceuticals blister.
Vll-l) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica, nanocomposites, dolomite, silica, silicates, glass, asbestos).
The presently claimed invention offers one or more of following advantages: WO 2022/096356 PCT/EP2021/079940 52 1. The multilayer film prepared in accordance with the method of the present invention exhibits high stability by reducing degradation induced by the high level of chlorine containing compounds. 2. The multilayer film prepared with the stabilizer mixtures of the present invention exhibit a substantial improvement in the elongation at break property of the film. 3. The articles prepared in accordance with the present invention are stable and has long lasting application by reducing degradation induced by the high level of chlorine containing compounds, hence use of these articles are economic.
In the following, specific embodiments of the presently claimed invention are described: 1. A method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture comprising: (i) at least one compound (A) selected from general formula (I), genera formula (II), general formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C1-C12 alkyl, 0!-012 alkyloxy, substituted or unsubstituted C5-C12 cycloalkyl and C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), WO 2022/096356 PCT/EP2021/079940 or H3C CH, CH3z C h3 A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and is an integer in the range of 1 to 20 and the repeating units are the same or different, compound (A) of general formula (II) wherein x! and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, compound (A) of general formula (III) a O—C-----& wherein is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl; and compound (A) of general formula (IV) WO 2022/096356 PCT/EP2021/079940 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted or unsubstituted C3 to C20 alkyl, and C3 to C20 alkylidene, X is C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber; and (iii) at least one metal hydroxide. 2. The method according to embodiment 1, wherein the organic material is selected from inear low-density polyethylene, low-density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer, polypropylene homopolymer and polypropylene copolymer. 3. The method according to embodiment 1, wherein the organic material is selected from inear low-density polyethylene, low-density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-butyl acrylate copolymer. 4. The method according to embodiment 1, wherein the chlorine containing compound is selected from an agrochemical compound and a bleaching agent.
. The method according to embodiment 1, wherein A! is selected from linear or branched, substituted or unsubstituted C2-C8 alkylene and substituted or unsubstituted cyclohexylene, A2 is independently selected from H, linear or branched, substituted or unsubstituted C!-C8 alkyl, C1-C12alkyloxy, substituted or unsubstituted cyclohexyl and cyclohexyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted 0!-08 alkyl or a group of the formula (a-1) or A3 and A4, together with the nitrogen atom to which they are bonded, form a morpholinyl group, and a is an integer in the range of 1 to 10.
WO 2022/096356 PCT/EP2021/079940 55 6. The method according to one or more of embodiments 1 to 5, wherein the stabilizer mixture comprises: (i) at least one compound (A) selected from general formula (I), general formula (II), genera formula (III), general formula (IV), and mixtures thereof compound (A) of general formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7 cycloalkylene and C1-C4alkylenedi(C 5-C7cyclo alkylene), A2 is independently selected from linear or branched, substituted orunsubstituted C!-C12 alkyloxy, and substituted or unsubstituted C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c chN—A2(a-1) ch3z c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, compound (A) of general formula (II) WO 2022/096356 PCT/EP2021/079940 (II) wherein x!and x 2 is independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, - compound (A) of general formula (III) (III) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl; and - compound (A) of general formula (IV) (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, WO 2022/096356 PCT/EP2021/079940 57 Y3 is independently selected from linear or branched, substituted or unsubstituted C3 to C20 alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber, and (iii) at least one metal hydroxide. 7. The method according to one or more of embodiments 1 to 6, wherein the stabilizer mixture comprises: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), genera formula (IV), and mixtures thereof, compound (A) of general formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18alkylene, substituted or unsubstituted C5-C7 cycloalkylene, and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted 0!-012 alkyl, and substituted or unsubstituted C5-C12 cycloalkyl, A3 and A4 are independently selected from H, linear or branched, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c ch3 ch3 c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and WO 2022/096356 PCT/EP2021/079940 58 a is an integer in the range of 1 to 20 and the repeating units arethe same or different, compound (A) of general formula (II) (II) wherein x!and x 2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, compound (A) of general formula (III) (HI) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl; and compound (A) of general formula (IV) WO 2022/096356 PCT/EP2021/079940 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted orunsubstituted C3 to C20 alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber; and (iii) at least one metal hydroxide. 8. The method according to one or more of embodiments 1 to 7, wherein the compound (A) is at east one compound selected from the formula (A-l), (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), and (A-8) (A-l), N H9C4-N------------------------------------- N--------- (CH2)6----- N----- N^,N J. ־؛ c، J ־ h ؛ JLJ N --------- --------------------------- N—C4Hg N^,N .CHa T H3Cj}zCH3 ■CHa N-C4H9h3C/ WO 2022/096356 PCT/EP2021/079940 (A-2), (A-3) wherein a is an integer in the range of 1 to 10, (A-4), WO 2022/096356 PCT/EP2021/079940 (A-6) WO 2022/096356 PCT/EP2021/079940 (A-7), and (A-8) wherein n is 2. 9. The method according to one or more of embodiments 1 to 7, wherein the compound (A) is a compound of formula (A-9) WO 2022/096356 PCT/EP2021/079940 wherein a is an integer in the range of 1 to 10.
. A stabilizer mixture comprising: (i) at least one compound (A) selected from the general formula (A-l), general for-mula (A-2), general formula (A-4), general formula (A-5), general formula (A-6), general formula (A-7), and general formula (A-8) (A-l), (A-2), (A-4), WO 2022/096356 PCT/EP2021/079940 (A-5); (A-6) WO 2022/096356 PCT/EP2021/079940 (A-7), and (A-8) wherein n is 2, (ii) at least one UV absorber; and (iii)at least one metal hydroxide. 11. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to embodiment 10, wherein the at least one UV absorber is selected from 2-(2'-hydroxy phenyl )benzotriazo les, 2-hydroxy benzophenones, 2-(2-hydroxy phenyl)-1,3,5-triazines and mixtures thereof. 12. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to embodiments 10 or 11, wherein the 2-(2'-hydroxyphenyl)benzotriazole is WO 2022/096356 PCT/EP2021/079940 66 selected from 2-(2H-benzotriazol-2-yl)-4,6-bis(l-methyl-l-phenylethyl)phenol, 2-(2'- hydroxy-5'-methyl phenyl)-benzotriazole, 2 - (3', 5'-di-tert-butyl -2'-hydroxy phenyl) ben-zotriazole, 2 - (5'-tert-buty I-2'-hydroxy phenyl) benzotriazo Ie, 2-(2'-hydroxy-5'- (1,1,3,3- tetramethylbutyl)phenyl)benzotriazole, 2 - (3', 5'-di-tert-butyl -2'-hydroxy phenyl) -5-ch loro-benzotriazo le,2-(3'-tert-butyl -2'-hydroxy-5'-methyl phenyl) -5-ch I oro-benzotria- zole, 2-(3'-sec-buty I-5'-tert-butyl -2'-hydroxy phenyl) benzotriazole, 2-(2'-hydroxy-4'-oc- tyloxy phenyl) benzotriazole, 2 - (3', 5'-di-tert-a my I-2'-hydroxyphenyl) benzotriazole, 2-(3',5'-bis-(a , a -di methyl benzyl) -2'-hydroxy phenyl )ben zotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octy I oxycar bony I ethyl) phenyl) -5-chloro-benzotriazole, 2-(3'-tert-butyl- 5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl -2'-hydroxy-5'- (2-meth oxycar bony I ethyl) phenyl) benzotriazo Ie, 2-(3'-tert-butyl -2'-hydroxy-5'- (2-octyl oxycarbonylethyl) phenyl) benzotriazole, 2-(3'-tert-bu- ty I-5'-[2-(2-ethyl hexyloxy) car bony I ethyl] -2'-hydroxy phenyl) benzotriazo Ie, 2-(3'-do-decy I-2'-hydroxy-5'-methyl phenyl) benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-iso- octyl oxycarbonylethyl) phenyl benzotriazo Ie, 2,2'-methylene-bis[4-(l,l,3,3-tetramethyl- butyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl- 5'-(2 - m ethoxyca rbonyl ethyl) -2'-hydroxy phenyl] -2 H-benzotriazole with polyethylene glycol 300; [r—CH2CH2—COO-CH2CH29־— , where R = 3'-tert-butyl-4'-hydroxy-5'- 2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(ct , a -dimethylbenzyl)-5'-(l,l,3,3-tetra- methyl butyl)-phenyl] benzotriazole; and 2-[2'-hydroxy-3'-(l, 1,3,3-tetra methyl butyl)-5'-( a , a -dimethylbenzyl)-phenyl]benzotriazole, and mixtures thereof. 13. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 12, wherein the 2-hydroxybenzophe- none is selected from 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4- benzyloxy, 4,2',4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivatives and mixtures thereof. 14. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 13, wherein the 2-(2-hydroxyphenyl)- 1,3,5-triazine is selected from 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-l,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethyl phenyl)-1,3,5-triazine, 2-(2,4-dihy- droxyphenyI) -4,6-bis(2,4-dimethyl phenyl) -1,3,5-triazine, 2,4-bis(2-hydroxy-4-pro-py I-!oxy phenyl) -6-(2,4-di methyl phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)- 4,6-bis(4-methy I phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4- di methyl phenyl) -1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dime-thy I phenyl) -1,3,5-triazine, 2-[2-hydroxy-4- (2-hydroxy-3-butyl oxy pro poxy) phenyl] -4,6- bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3- WO 2022/096356 PCT/EP2021/079940 67 octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazine, 2-[4-(do-decyloxy/tridecyloxy-2-hyd roxy propoxy) -2-hydroxy phenyl] -4,6-bis (2,4-di me- thy I phenyl) -1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-di methyl phenyl)-l,3,5-triazi ne, 2-(2-hydroxy-4-hexyl oxy) phenyl-4,6-diphe- nyI -1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-l,3,5-triazine, 2,4,6- tris [2-hydroxy-4-(3-butoxy-2-hydroxy pro poxy) phenyl] -1,3,5-triazine, 2-(2-hydroxy-phenyl)-4-(4-methoxyphenyl)-6-phenyl-l,3,5-triazine, 2-{2-hydroxy-4- [3-(2-ethyl hexy 1-1-oxy) -2-hyd roxy propyloxy]phenyl}-4, 6-bis(2,4-di-! methyl phenyl)-!, 3,5-tri- azine, 2,4-bis(4-[2-ethy I hexyl oxy] -2-hydroxy phenyl)-6-(4-methoxyphenyl)-l,3,5-tria- zine, 2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl] -1,3,5-triazine, Do- decanedioic acid, l,12-bis[2-[4-(4,6-diphenyl-l,3,5-triazin-2-yl)-3-hydroxyphenoxy] ethyl] ester and mixtures thereof.
. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 14, wherein the at east one metal hy- droxide is selected from hydrotalcite and magnesium hydroxide. 16. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of claims 10 to 15, wherein the hydrotalcite is selected from magnesium aluminum hydroxide carbonate hydrate, and zinc aluminum hydroxide car- bonate hydrate. 17. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 16, wherein the weight ratio of the at east one compound (A) to the at least one UV absorber is in the range of 1:1 to 20:1. 18. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 17, wherein the weight ratio of the at east one compound (A) to the at least one metal hydroxide is in the range of 1:10 to 10:1. 19. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 18, wherein the weight ratio of the at east one UV absorber to the at least one metal hydroxide is in the range of 10:1 to 1:20.
. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 19, wherein the stabilizer mixture further comprises at least one light stabilizers. 21. The method according to one or more of embodiments 1 to 9 or the stabilizer mixture according to one or more of embodiments 10 to 20, wherein the light stabilizer is se- ected from bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-pi- peridy I) succinate, bis(l,2,2,6,6-penta methyl -4-piperidyl)sebacate, bis (1-octyl oxy- WO 2022/096356 PCT/EP2021/079940 68 2,2,6,6-tetra methy I-4-pi peridy I) sebacate, bis (1,2,2,6,6-penta methyl -4-piperidyl) n-bu- tyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of l-(2-hydroxyethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octyla- mino-2,6-dichloro-l,3,5-triazine, tris (2,2,6,6-tetra methyl -4-piperidyl) nitrilotriacetate,tetra kis (2,2,6,6-tetra methyl -4-pi peridy I)-1,2,3,4-butanetetracar boxy I ate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetrame-thylpiperazinone), 4-benzoy I-2,2,6,6-tetra methyl pi per- idine, 4-steary I oxy-2,2,6,6-tetra methy I pi peridi ne, bis (1,2,2,6,6-penta methyl piperidyl)- 2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetrame- thyl-l,3,8-triazaspiro [4.5]decane-2,4-dione, bis(1-octyloxy-2, 2,6,6-tetra methyl pi-peridyl)sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4- morpholino-2,6-dichloro-l,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butyla- mino-2,2,6,6-tetramethylpiperidyl)-l,3,5-triazine and l,2-bis(3-aminopropyla- mino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-l,2,2,6,6-pentame- thylpiperidyl)-l,3,5-triazine and l,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-do- decyl-7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-l- (2,2,6,6-tetra methyl-4-pi peridy I) pyrrol id ine-2,5-d io ne, 3-dodecyl-l -(1,2,2,6,6-pen-tamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stea- ryloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4-pi- peridyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-l,3,5-triazine, a condensate of l,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-l,3,5-triazine and 4-butyl am in 0-2,2,6,6-tetra methyl pi peridi ne;; N-(2,2,6,6-tetramethyl-4-piperidyl)- n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyI -4-piperidyI)-n-dodecylsuccinimide, 2- undecyl-7, 7,9,9-tetramethyl-l-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction prod- uct of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-penta methy I-4-pi peridy I oxycarbonyl) -2-(4-meth oxy- phenyl) ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexameth- ylenediamine, a diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentame- thyl-4-hydroxypi peridi ne, poly [methyl propyl-3-oxy-4-(2,2,6,6-tetramethyl-4-pi-peridyl)]siloxane, a reaction product of maleic acid anhydride- a -olefin copolymer with 2,2,6,6-tetra methy I-4-a mi nopiperidine or 1,2,2,6,6-penta m ethy I -4-a mi nopiperidine, 2,4-bis[N-(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2- hydroxyethyl) a mi no- 1,3,5-triazine,, 5-(2-ethy I hexanoy I) oxy methy I-3,3,5-tri methy I-2-morpholinone, Sanduvor, 5 - (2-ethy I hexa noy l)oxy methy I-3,3,5-tri methy I-2 -mor pho-inone, the reaction product of 2,4-bis[(l-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butyla- mino]-6-chloro-s-triazine with N,N’-bis(3-aminopropyl)ethylenediamine), l,3,5-tris(N- cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine, 1,3,5- WO 2022/096356 PCT/EP2021/079940 69 tris(N-cyclohexyl-N-(l,2,2,6,6-pentamethylpiperazine-3-one-4-yl)amino)-s-triazine, and mixtures thereof. 22. A composition comprising: I. an organic material, and II. a stabilizer mixture according to one or more of embodiments 10 to 21. 23. The composition according to embodiment 22, further comprising at least one additive selected from the antioxidants, slip agents, anti-block agents, thermal fillers, pigments, anti-fog and anti-mist agents. 24. The composition according to embodiments 22 or 23, wherein the weight ratio of the organic material to the stabilizer mixture is in the range of 0.005:10%.
. An article comprising the composition according to one or more of embodiments 22 to 24. 26. The article according to embodiment 25, which is a monolayer film or a multilayer film of three to twelve layers. 27. The article according to embodiments 25 or 26, wherein the multilayer film contains at east one compound (A) as defined in embodiment 1 in at least one layer, and at least one compound of the UV absorber and a compound of the at least one metal hydroxide as defined in embodiment 1 independently in another layers. 28. The article according to one or more of embodiments 25 to 27, which is a greenhouse film cover, mulch film, artificial turfs, or geomembrane. 29. The article according to one or more of claim embodiments 25 to 28, wherein the green- house film cover, mulch film, artificial turf, or geomembrane is in contact with an agro- chemical compound or bleaching agent.
. Use of the stabilizer mixture according to one or more of embodiments 10 to 21 for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having the chlorine content in the range of 100 to 600 ppm. 31. The composition according to one or more of embodiments 22 to 24 or the use according to embodiment 30, wherein the organic material is selected from linear low-density pol- yethylene, low-density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer, polypropylene homopolymer and poly- propylene copolymer, preferably linear low-density polyethylene, low-density polyeth- ylene, high density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-buty acrylate copolymer.
WO 2022/096356 PCT/EP2021/079940 70 32. The use according to embodiments 30 or 31, wherein the chlorine containing compound is selected from an agrochemical compound, and a bleaching agent.
The following examples illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise.
EXAMPLES Compounds: Compound Bis(l- undecan oxy-2,2,6,6-tetra methyl pi peridin-4-y !)carbonate Compound (A-3) wherein a is an integer in the range of 1 to 10.
Compound (A-4): 1 - (2 - hydroxy-2- methyl pro poxy) -2,2,6,6-tetra methyl pi peridi ne-4-y I octadecenoate WO 2022/096356 PCT/EP2021/079940 71 Compound 2-(2'-hydroxy-5'- (1,1,3,3-tetra methyl butyl) phenyl) benzotriazo Ie Compound (B-2): 2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl] -1,3,5-triazine Compound (B-3): Condensate of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid h3c ch3 N—CH2-CH2-OOC-CH2CH2-CO----- h3c ch3bwherein b is a number from 2 to 10.
Compound (C-l): (CAS number: 012304-65-3 or 11097-59-9) WO 2022/096356 PCT/EP2021/079940 72 Hydrotalcite (Magnesium aluminum hydroxide carbonate hydrate) Compound Magnifin H-5 IV (is aminosilane surface treated) (CAS number: 1309-42-8) Magnesium hydroxide Compound (C-3): Kisuma 10A (CAS number: 1309-42-8) Magnesium hydroxide A) Preparation of the film samples: Stabilization of LDPE (low density polyethylene) multi-layer films: Formulations containing LDPE powder (Polimeri Europa Riblene" FC 30, characterized by a density of 0.922 g/cm 3 and a melt flow index (190° C/2.16Kg) of 0.27 g/lOmin), 0.04% by weight, relative to the weight of the LDPE, of tris{2,4-di-tert-butyl phenyl} phosphite, 0.01% by weight, relative to the weight of the LDPE, of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and the stabilizer mixtures indicated in Tables 1 and 2, were prepared. The formulations were mixed in a turbo- mixer. Each formulation was extruded at a maximum temperature of 200° C in a lab-scale single-screw Collin extruder (0 42mm, L/D=25). Then, each final formulation was blown in a lab-scale Collin' " 5-layer blow-extruder (0 20-25-30mm, L/D 25), at a maximum temperature of 210° C, to give a 5-layer film having the same formulation in all layers. The overall thick- ness of the film was 160 p.m (50 p.m - 15 p.m - 30 p.m - 15 p.m - 50 ^m).
B) Test method A A bleach treatment was carried out on the prepared films before artificial weathering. Speci- mens of the films for each formulation were treated with sodium hypochlorite (NaCIO)-H 2O 1:4 solution for 24 hours at t=0 hours. The chlorine determination was performed immediately after the treatment and at every recall (every 1000 hours exposure in artificial weathering) to determine the next treatment. The chlorine content was determined using oxidative pyrolysis and coulometry.
WO 2022/096356 PCT/EP2021/079940 73 After the agrochemical treatment, the film specimens for each formulation were exposed in an Atlas Weather-O-Meter (WOM, as per ASTM G155, 0.35 W/m2 at 340 nm, dry cycle), for accelerated light weathering. Specimens of the film samples were taken at defined intervals of time after exposure and underwent tensile testing. The residual tensile strength was meas- ured, by means of a Zwick® Z1.0 constant velocity tensiometer (as per modified ISO 527), in order to evaluate the decay of the mechanical properties of the film samples, as a conse- quence of the polymer degradation after its oxidation.
The test results are listed in Tables 1 and 2.
Table 1: NOR HALS [Compound of (A-3)] and UV Package with and without Hydrotalcite Film samples contaminated with 400-500 ppm chlorine after each treatment and exposed in a WOM.
Stabilizer mixture (weight-% based on polymer composition)Time until retained elon- gation at break in hours is 50% of the initial valueExample (Comparative)0.55% of Compound (A-3)0.049% of Compound (B-l)0.015% of Compound (B-2)3489 Example 2 0.55% of Compound (A-3) 0.049% of Compound (B-l) 0.015% of Compound (B-2) 0.3% of Compound (C-l) 3724 Example 3 0.55% of Compound (A-3) 0.049% of Compound (B-l) 0.015% of Compound (B-2) 0.6% of Compound (C-l) 3713 Example 4 0.55% of Compound (A-3) 0.049% of Compound (B-l) 0.015% of Compound (B-2) 0.6% of Compound (C-2) 3831 Example 5 0.55% of Compound (A-3) 0.049% of Compound (B-l) 0.015% of Compound (B-2) 0.6% of Compound (C-3) 3857 Example 6 0.55% of Compound (A-3) 0.049% of Compound (B-l) 0.015% of Compound (B-2) 0.3% of Compound (C-l) 3827

Claims (19)

WO 2022/096356 PCT/EP2021/079940 75 CLAIMS
1. A method for stabilizing an organic material by reducing degradation induced by a chlorine containing compound having a chlorine content in the range of 100 to 600 ppm, wherein the method comprises incorporating into the organic material a stabilizer mixture com- prising: (i) at least one compound (A) selected from general formula (I), general formula (II), general formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7cyclo alkylene), A2 is independently selected from H, linear or branched, substitutedor unsubstituted C!-C12 alkyl, C!-C12 alkyloxy, substituted or un- substituted C5-C12cycloalkyl and C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substi- tuted or unsubstituted C!-C12alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c ch, ch3z c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units arethe same or different, WO 2022/096356 PCT/EP2021/079940 76 compound (A) of general formula (II) (II) wherein x!and x2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, compound (A) of general formula (III) (III) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, 10 Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl; and compound (A) of general formula (IV) (IV) wherein WO 2022/096356 PCT/EP2021/079940 77 Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted or un- substituted C3 to C20alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber; and (iii) at least one metal hydroxide.
2. The method according to claim 1, wherein the organic material is selected from linear low- density polyethylene, low-density polyethylene, high density polyethylene, ethylene-viny acetate copolymer, ethylene-butyl acrylate copolymer, polypropylene homopolymer and polypropylene copolymer.
3. The method according to claims 1 or 2, wherein the stabilizer mixture comprises: (i) at least one compound (A) selected from general formula (I), general formula (II), gen- era formula (III), general formula (IV), and mixtures thereof compound (A) of general formula (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18 alkylene, substituted or unsubstituted C5-C7cycloalkylene and C1-C4alkylenedi(C 5-C7 cyclo alkylene), A2 is independently selected from linear or branched, substituted orunsubstituted C!-C12 alkyloxy, and substituted or unsubstituted C5-C12cycloalkyloxy, A3 and A4 are independently selected from H, linear or branched, substi- tuted or unsubstituted C!-C12alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), WO 2022/096356 PCT/EP2021/079940 78 h3c ch. CH3z C h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units are the same or different, compound (A) of general formula (II) o—c—& wherein x! and x2 is independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, compound (A) of general formula (III) wherein is linear or branched, substituted or unsubstituted linear or branched, substituted or unsubstituted C3 to C20 alkyl, 2is linear or branched, substituted or unsubstituted C! to C30 alkyl; and compound (A) of general formula (IV) WO 2022/096356 PCT/EP2021/079940 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted or un- substituted C3 to C20alkyl, and C3 to C20 alkylidene, X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber, and (iii)at least one meta hydroxide.
4. The method according to one or more of claims 1 to 3, wherein the stabilizer mixture comprises: (i) at least one compound (A) selected from general formula (I), general formula (II), genera formula (III), general formula (IV), and mixtures thereof, compound (A) of general formula (I) (I) wherein A! is selected from linear or branched, substituted or unsubstitutedC2-C18alkylene, substituted or unsubstituted C5-C7cycloalkylene, and C1-C4alkylenedi(C 5-C7 cyclo alkylene), WO 2022/096356 PCT/EP2021/079940 a2 A3and A4 80 is independently selected from H, linear or branched, substituted or unsubstituted 0!-012 alkyl, and substituted or unsubstituted C5-C12 cycloalkyl, are independently selected from H, linear or branched, substi- tuted or unsubstituted C!-C12 alkyl, substituted or unsubstituted C5-C12 cycloalkyl and a group of the formula (a-1), h3c ch3A_,CH c h3 or A3 and A4, together with the nitrogen atom to which they are bonded, form a5- to 10-membered heterocyclic ring; and a is an integer in the range of 1 to 20 and the repeating units are the same or different, compound (A) of general formula (II) x, o--c—& wherein x! and x2 are independently selected from linear or branched, substituted or unsubstituted C! to C30 alkyloxy, compound (A) of general formula (III) wherein WO 2022/096356 PCT/EP2021/079940 81 Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y2 is linear or branched, substituted or unsubstituted C! to C30 alkyl; and compound (A) of general formula (IV) 5 (IV) wherein Y! is linear or branched, substituted or unsubstituted C3 to C20alkyl, Y3 is independently selected from linear or branched, substituted or un- substituted C3 to C20alkyl, and C3 to C20 alkylidene, 10 X is linear or branched, substituted or unsubstituted C2 to C5 alkyl, n is an integer in the range of 1 to 8, and (ii) at least one UV absorber; and (iii)at least one metal hydroxide.
5. The method according to one or more of claims 1 to 4, wherein the compound (A) is at least one compound selected from the formula (A-l), (A-2), (A-3), (A-4), (A-5), (A-6), (A- 7), and (A-8) (A-l), WO 2022/096356 PCT/EP2021/079940 (A-2), (A-3) 5 wherein a is an integer in the range of 1 to 10, (A-4), WO 2022/096356 PCT/EP2021/079940 (A-6) WO 2022/096356 PCT/EP2021/079940 (A-7), and 5 (A-8) wherein n is 2.
6. The method according to one or more of claims 1 to 5, wherein the compound (A) is a compound of formula (A-9) WO 2022/096356 PCT/EP2021/079940 wherein a is an integer in the range of 1 to 10.
7. A stabilizer mixture comprising: 5 (i) at least one compound (A) selected from the general formula (A-l), general formula(A-2), general formula (A-4), general formula (A-5), general formula (A-6), genera formula (A-7), and general formula (A-8) (A-l), (A-2), (A-4), WO 2022/096356 PCT/EP2021/079940 (A-5); (A-6) WO 2022/096356 PCT/EP2021/079940 (A-7), and 5 (A-8) wherein n is 2, (ii) at least one UV absorber; and (iii)at least one metal hydroxide.
8. The method according to one or more of claims 1 to 6 or the stabilizer mixture according to claim 7, wherein the at least one UV absorber is selected from 2-(2'-hydroxy- phenyl) benzotriazoles, 2-hydroxy benzo phen ones, 2-(2-hydroxy phenyl) -1,3,5-triazines and mixtures thereof.
9.WO 2022/096356 PCT/EP2021/079940 88 9. The method according to one or more of claims 1 to 6 or the stabilizer mixture according to claims 7 or 8, wherein the at least one metal hydroxide is selected from hydrotalcite and magnesium hydroxide.
10. The method according to one or more of claims 1 to 6 or the stabilizer mixture according to one or more of claims 7 to 9, wherein the hydrotalcite is selected from magnesium alu- minum hydroxide carbonate hydrate, and zinc aluminum hydroxide carbonate hydrate.
11. The method according to one or more of claims 1 to 6 or the stabilizer mixture according to one or more of claims 7 to 10, wherein the weight ratio of the at least one compound (A) to the at least one UV absorber is in the range of 1:1 to 20:1, the weight ratio of the at east one compound (A) to the at least one metal hydroxide is in the range of 1:10 to 10:1, and the weight ratio of the at least one UV absorber to the at east one metal hydroxide is in the range of 10:1 to 1:20.
12. The method according to one or more of claims 1 to 6 or the stabilizer mixture according to one or more of claims 7 to 11, wherein the stabilizer mixture further comprises at least one light stabilizers.
13. A composition comprising: I. an organic material, and II. a stabilizer mixture according to one or more of claims 7 to 12.
14. The composition according to claim 13, further comprising at least one additive selected from the antioxidants, slip agents, anti-block agents, thermal fillers, pigments, anti-fog and anti-mist agents.
15. The composition according to claims 13 or 14, wherein the weight ratio of the organic ma- terial to the stabilizer mixture is in the range of 0.005:10%.
16. An article comprising the composition according to one or more of claims 13 to 15.
17. The article according to claim 16, which is a monolayer film or a multilayer film of three to twelve layers, wherein the multilayer film contains at least one compound (A) as defined in claim 1 in at least one layer, and at east one compound of the UV absorber and a com- pound of the at east one metal hydroxide as defined in claim 1 independently in another ayers.
18. The article according to claims 16 or 17, which is a greenhouse film cover, mulch film, artificial turfs, or geomembrane.
19. Use of the stabilizer mixture according to one or more of claims 7 to 12 for stabilizing an organic material by reducing degradation induced by a chlorine containing compound hav- Ing the chlorine content in the range of 100 to 600 ppm.
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